Preparation of Cyclic Imides from Alkene-Tethered Amides: Application of Homogeneous Cu(II) Cite This: RSC Adv., 2020, 10, 7698 Catalytic Systems†
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RSC Advances View Article Online PAPER View Journal | View Issue Preparation of cyclic imides from alkene-tethered amides: application of homogeneous Cu(II) Cite this: RSC Adv., 2020, 10, 7698 catalytic systems† Zhenghui Liu, *a Peng Wang,bc Hualin Ou,b Zhenzhong Yan,a Suqing Chen,a Xingxing Tan,bd Dongkun Yu,d Xinhui Zhaod and Tiancheng Mu *d A Cu-based homogeneous catalytic system was proposed for the preparation of imides from alkene- Received 11th December 2019 tethered amides. Here, O acted as a terminal oxidant and a cheap and easily available oxygen source. Accepted 5th February 2020 2 The cleavage of C]C bonds and the formation of C–N bonds were catalyzed by Cu(II) salts with proper DOI: 10.1039/c9ra10422d nitrogen-containing ligands under 100 C. The synthesis approach has potential applications in rsc.li/rsc-advances pharmaceutical syntheses. Moreover, scaled-up experiments confirmed the practical applicability. found to be able to achieve such preparations. In 2016, Shimizu Creative Commons Attribution 3.0 Unported Licence. 1. Introduction et al. completed the direct synthesis of cyclic imides by using Cyclic imides are becoming increasingly popular in the phar- carboxylic anhydrides and amines using Nb2O5 as a water- maceutical eld.1–5 Some drug molecules bearing cyclic imide tolerant Lewis acid catalyst without solvents (Scheme 2c).12 In structures are shown in Scheme 1. Among them, lenalidomide, 2017, Gaunt et al. set up a Co-catalyzed carbonylative cyclization carmofur, uorouracil, and aminoglutethimide are antineo- procedure of unactivated, aliphatic C–H bonds with a combination 13 plastic drugs; utamide is an antiu drug; and phensuximide, of Co(acac)2, PhCOONa, Ag2CO3, PhCl, and CO (Scheme 2d). phenytoin, and glutethimide are antiepileptic, antiarrhythmic, In addition, other methods such as electrocatalysis and and sedative-hypnotic drugs, respectively. The preparations of photocatalysis could also be used in this transformation 14,15 This article is licensed under a imides and cyclic imides have been paid much attention over (Scheme 2e and f). the years.6–9 As shown in Scheme 2, certain methods were The valid and selective oxidation of organic compounds gradually proposed. In 2005, Higuchi et al. proposed an oxida- offers the opportunity for the streamlined conversion of simple tion method of amides with 2,6-dichloropyridine N-oxide cata- precursors into value-added products.16 Oxidation reactions, Open Access Article. Published on 21 February 2020. Downloaded 10/3/2021 12:09:27 AM. lyzed by ruthenium porphyrin in benzene at a low temperature together with polymerizations and carbonylations, constitute of 40 C overnight (Scheme 2a).10 Aer that, more nonnoble the largest industrial applications in the eld of homogeneous metals were employed in this type of transformation. In 2009, catalysis, and substantial value-added bulk and ne chemicals Beller et al. translated hex-3-yne into cyclic imides with CO and can be fabricated through this technology.17 With the superi- ffi NH3 catalyzed by [Fe3(CO)12] in THF at 120 C for 16 h, which ority of environmental compatibility, low cost, and high e - was the rst report on the iron-catalyzed synthesis of succini- ciency, O2 is becoming a frequently used oxidant in both mides via the carbonylation of diverse internal and terminal experimental and industrial scenarios.18,19 With regard to green alkynes with amines or ammonia to achieve good selectivity and high activity (Scheme 2b).11 Later, metallic oxides were also aSchool of Pharmaceutical and Materials Engineering, Taizhou University, Taizhou 318000, Zhejiang, China. E-mail: [email protected] bBeijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China cKey Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, Henan, China dDepartment of Chemistry, Renmin University of China, Beijing 100872, China. E-mail: [email protected] † Electronic supplementary information (ESI) available: Tables S1–S15, Scheme S1, ESI-MS measurement, NMR spectra of substrates, products and intermediate. See DOI: 10.1039/c9ra10422d Scheme 1 Pharmaceutical molecules with cyclic imide structures. 7698 | RSC Adv.,2020,10, 7698–7707 This journal is © The Royal Society of Chemistry 2020 View Article Online Paper RSC Advances employed in the oxidation of alkene-tethered amide 1a into cyclic imide 2a in MeCN at 100 CinanO2 environment under atmospheric pressure. Cu(acac)2 with ligand A (neocuproine) exhibited outstanding catalytic performance with the highest 2a yield of 85%, while the others behaved moderately or even badly under otherwise identical conditions. Phosphine ligands were not expected to be efficient in an O2 atmosphere due to inacti- vation caused by oxidation.18 Further, they indeed provided no yields (Table 1; for detailed yields, see ESI, Tables S2–S11†). In addition, all the tested Cu salts satisfactorily performed with $ yields over 75% (e.g., Cu(BF4)2 2H2O: 82%; CuF2: 81%; CuCl2- $ 2H2O: 80%), among which Cu(acac)2 gave the highest yield of 2a (Table S12†). 2.2 Optimized dosage of Cu(acac)2 and neocuproine Aer conrming the suitable combination of Cu(acac)2 and neocuproine, the optimized ratio of Cu(acac)2 and neocuproine ligand was explored, as shown in Fig. 1A. Originally, the relative molar ratio of [Cu] vs. ligand was set at 1 vs. 1. As expected, the yields were higher when the loading values were higher (from 20% at 0.4 equiv. : 0.4 equiv. to 46% at 1 equiv. : 1 equiv.). However, aer each loading was above 1 equiv., the yields Creative Commons Attribution 3.0 Unported Licence. stopped increasing (maintaining 46% at 1.5 equiv.). Then, the loading of neocuproine was adjusted further as the dosage of Cu(acac)2 was xed at 1 equiv. As shown in Fig. 1A, when the loadings of neocuproine were 0.8, 1.0, 1.2, and 1.5 equiv., the yields were 31%, 46%, 68%, and 85%, respectively. This implied the strong dependency of neocuproine dosage in the system. However, a further increase in the neocuproine dosage to 1.8 equiv. did not help in increasing the yield. Finally, the loading was doubled as 2 equiv. : 3 equiv., and the yield was still This article is licensed under a Scheme 2 Different strategies for the syntheses of cyclic imides. unimproved. Therefore, the optimized dosage of Cu(acac)2 and neocuproine was 1 equiv. vs. 1.5 equiv. ff Open Access Article. Published on 21 February 2020. Downloaded 10/3/2021 12:09:27 AM. 2.3 E ects of solvents and sustainable chemistry, oxidants such as inorganic salts, ff IBX, oxone, BQ TBHP, DDQ, or PhI(OAc)2 su er from many Solvents acted as the reaction media and intensively in uenced problems such as waste disposal, high cost, and poor atom the catalytic reactions.30–34 The effects of nine representative economy. solvents on the catalytic reaction were tested, and the results Encouraged by the recently published articles and our were summarized, as shown in Fig. 1B. Five nonpolar solvents interest in nonnoble-metal-catalyzed oxidization and cycliza- were tested. Tetrahydrofuran (THF) and acetone showed nearly tion reactions, herein, we developed an efficient, copper-based no activity in the system. Nitromethane (MeNO2) and 1,4- catalytic system comprising commercially available Cu salts dioxane started to show some reactive abilities. Surprisingly, and a bidentate nitrogen ligand for the preparation of cyclic when the solvent was switched to MeCN, the highest yield was imides from alkene-tethered amides in acetonitrile (MeCN) 85%. In addition, three high-boiling-point polar aprotic 20–22 under atmospheric O2 at 100 C. solvents, namely, dimethyl sulfoxide (DMSO), dimethyl form- amide (DMF), and 1,3-dimethyl-2-imidazolidinone (DMI), were tested, but they yielded nearly no products. Finally, we tried 2. Results and discussion ethanol (EtOH) as a protic solvent, and it showed a medium 2.1 Screening of metal salts and ligands yield. Without doubt, MeCN was considered to be the most Metal salts coordinated with specic ligands exhibit excellent suitable solvent for this system. catalytic abilities.23–29 In the initial set of experiments, a series of ff frequently used metal salts coordinated with ligands 2.4 E ects of temperature containing N, P, or other elements were tested, and the results To gain more specic information regarding the catalytic are shown in Table 1. Here, 10 types of transition metal salts (Fe, system, the reaction temperatures were set from 30 to 110 C Co, Ni, Cu, Zn, Mn, Pd, Ru, Rh, and Ir salts) with 22 types of (shown in Fig. 1C). Here, 30 and 40 C were too low to provide ligands (for detailed information, see ESI, Table S1†) were sufficient energy for the reaction. Temperatures ranging from This journal is © The Royal Society of Chemistry 2020 RSC Adv.,2020,10,7698–7707 | 7699 View Article Online RSC Advances Paper Table 1 Metal-catalyzed oxygenation of alkene-tethered amides to 5-oxo-4-phenylpyrrolidine-2-carbaldehyde) was detected and a cyclic imides recorded (shown in Fig. 1D). A clear initial increase in the aldehyde concentration was observed, and consumption subsequently occurred. In addition, the amount of 1a sharply decreased in the initial phase (for detailed information of the quantitative data, see ESI, Table S15†). 2.6 Effects of additives In order to further increase the yield and efficiency of the b Entry Metal salt Ligand Yield /% reaction, 10 types of additives were tested (shown in Table 2). c Unfortunately, none of them yielded better results. However, 1 FeCl3$6H2O A–V <1% $ – c the incorporation of H2O did not reduce the yield, which 2 Co(BF4)2 6H2O A V <5% – c 3 Ni(acac)2 A V <1% implied that the catalytic system was robust against water and – c 4 Cu(acac)2 A V Up to 85% therefore could be applied to more industrial scenes.